Polyhaloalkylpolythioalkyl ethers

ABSTRACT

ESTERS AND ETHERS OF THE FORMULA   ROXSMR&#39;&#39;   WHERE R&#39;&#39; REPRESENTS A POLYHALOALKYL GROUP HAVING 1 TO 2 CARBON ATOMS AND 3 TO 5 HALOGENS OF ATOMIC NUMBER 17 TO 35, AT LEAST ONE OF SAID HALOGENS BEING BONDED TO THE ALPHA CARBON ATOM, X IS ALKYLENE OF 1 TO 4 CARBON ATOMS AND M IS AN INTEGER VARYING FROM 2 TO 3, AND R IS AN ORGANIC RADICAL WHICH FORMS AN ESTER OR ETHER WITH THE REMAINDER OF THE MOLECULE. TYPICAL R GROUPS ARE HYDROCARBYL, PHOSPHORO, CARBONYL, OXYCARBONYL, SULFATE AND SULFONATE GROUPS. THESE ESTERS AND ETHERS ARE USEFUL AS FUNGICIDES.

United States Patent 3,584,054 POLYHALOALKYLPOLYTHIOALKYL ETHERS Joseph E. Moore, Richmond, Calif., assignor to Chevron Research Company, San Francisco, Calif.

No Drawing. Application Oct. 20, 1966, Ser. No. 588,009, now Patent No. 3,519,672, dated July 7, 1970, which 15 a continuation-impart of application Ser. No. 414,876, Nov. 30, 1964. Divided and this application Apr. 8,

1969, Ser. No. 844,686

Int. Cl. C07e 149/12 U.S. Cl. 260-608 4 Claims ABSTRACT OF THE DISCLOSURE Esters and ethers of the formula ROXS R' where R represents a polyhaloalkyl group having 1 to 2 carbon atoms and 3 to halogens of atomic number 17 to 35, at least one of said halogens being bonded to the alpha carbon atom, X is alkylene of 1 to 4 carbon atoms and m is an integer varying from 2 to 3, and R is an organic radical which forms an ester or ether with the remainder of the molecule. Typical R groups are hydrocarbyl, phosphoro, carbonyl, oxycarbonyl, sulfate and sulfonate groups. These esters and ethers are useful as fungici es.

CROSS REFERENCE TO RELATED APPLICATIONS This application is a divisional of copending application Ser. No. 588,009 filed Oct. 20, 1966, now US. Pat. 3,519,672, which in turn is a continuation-in-part of SN. 414,876, filed Nov. 30, 1964, now abandoned.

This invention relates to novel esters and ethers which contain a polyhalo (lower) alkylpolythioalkyl group and their use as fungicides.

The compounds of this invention may be represented by the general formula:

ROXS R' where R' represents a polyhaloalkyl group having 1 to 2 carbon atoms and 3 to 5 halogens of atomic number 17 to 35, at least one of said halogens being bonded to the alpha carbon atom, X is alkylene of 1 to 4 carbon atoms, m is an integer varying from 2 to 3, and R is an organic radical which combined with OXS R' forms an ether or ester. Halogens of atomic number 17 to 35 are chlorine and bromine. The alpha carbon atom of the polyhaloalkyl group is bonded to a sulfur of the polysultide (S group X is an alkylene group of from 1 to 4 carbons, e.g., methylene, ethylene, trimethylene, tetramethylene, isopropylene, 1,3-butylene, etc. The RO group is bonded to a primary carbon, that is, the carbon bonded to oxygen has two hydrogens. Preferred alkylene groups contain 2 to 3 carbons.

The esters and ethers of this invention may be considered to be derivatives of alcohols. Thus, in a broad sense R is an organic radical which forms a bond with oxygen and may be cleaved on hydrolysis to regenerate the alcohol as follows:

The R groups do not contribute significantly to the biological activity of the compounds of this invention. However, they may provide a means for special application or more attractive physical properties, e.g. hydrophobic, liphophilic, etc.

The R groups which form esters or ethers with OXS R' contain 1 to about 12 carbon atoms. Included among such groups are aliphatic and aromatic hydrocarbyl groups Patented June 8, 1971 'ice such as alkyl, alkenyl and phenyl, carbacyl, carbamoyl, 0,0-dialkyl phosphoro, alko-xy-carbonyl, thioalkoxycar bonyl, sulfate, sulfonate, borate and the like.

Among preferred R groups are the following:

where R is a halohydrocarbyl group having 0 to l halogens of atomic number 17 to 35 and 1 to about 8 carbon atoms or a halohydrocarbylamino group having 0 to 1 halogens of atomic number 17 to 35 and 1 to about 8 carbon atoms,

(UJYR3 where Y is a chalcogen atom of atomic number 8 to 16, i.e. O and S, and R is a halohydrocarbyl group having 0 to 1 halogens of atomic number 17 to 35 and 1 to about 8 carbon atoms or halophenylthioalkyl in which the halogen is of atomic number 17 to 35,

where R is a hydrocarbyl group of 1 to about 6 carbon atoms,

where R is OXS R' as defined above,

where 'R is OXS R as defined above or alkyl, or (f) alkyl of 1 to about 6 carbon atoms.

Examples of radicals which R may represent are alkyl such as methyl, ethyl, hexyl and octyl, butenyl, phenyl, benzyl, tolyl; haloalkyl such as chloromethyl, chloroethyl, bromopropyl and chloroamyl, chloropropenyl, bromophenyl, chlorobenzyl, 4-chloro-6-methylphcnyl; alkylamino such as methylamino, ethylamine, butylamino, hexylamino and chlorobutylamino, chlorophenylamine, bromophenylamino, 6-bromo-2-methyl-phenylamino and the like.

Examples of specific groups which R may be are methyl, ethyl, isopropyl, hexyl, octyl, chloroethyl, chloropropyl, bromoamyl, chlorophenyl, bromobenzyl, chlorobutenyl, 6-chloro-2-methylphenyl, chlorophenylthioethyl, bromophenylthiopropyl, chlorophenylthiobutyl and the like.

Examples of R are methyl, ethyl, propyl, hexyl, propargyl, butenyl and phenyl.

Illustrative of the novel compounds of this invention are the following compounds:

5- (trichloromethyldithio ethyl benzo ate;

5- (perchloroethyldithio ethyl acetate;

fl-( 1, 1,2-trichloroethyldithio ethyl benzoate;

5 1, l,2,Z-tetrachloroethyldithio ethyl N-ethylcarbamate;

,B-( 1,2, 2,2-tetrachloro ethyldithio )ethyl butyrate;

di-y- 1,1,2-trichloroethyldithio) -propyl carbonate;

'y-( 1,1,2,2-tetrachloroethyldithio)-propyl S-ethyl thiolcarbonate;

'y-(perchloroethyltrithio) -propyl hexanoate;

di-[ S- 1,2,2-trichloroethyldithio)ethyl] sulfate;

di- [,3- l,2,2,2-tetrachloroethyldithio ethyl] sulfate;

ethyl fi-( 1,1,2-trichloroethy1dithio) ethyl-sulfate;

butyl 'y-( 1-chloro-2,2-dibromoethyl)dithio propyl sulfate;

di 8- trichloromethyldithio ethyl] sulfite;

di ['y( 1, 1,2,2-tetrachloroethyldithio propyl] sulfite 0,0-dimethyl O- 13- (perchloro ethyldithio ethyl] phosphate;

0,0-dipropyl [B- 1,2,2-trichloroethyldithio ethyl] phosphate;

0,0-di-phenyl O- [fl-( 1, l,2,Z-tetrachloroethyldithio ethyl] phosphate;

0,0-dimethyl O- [p (perchloroethyldithio propyl] phosphate;

methyl-ptrichloromethyldithio) ethyl ether;

ethyl-' l,1,2,Z-tetrachloroethyltrithio)propyl ether;

amyl-v- (perchloroethyldithio)propyl ether, and hexyl-B- tribromomethyldithio propyl ether.

Applicants novel compounds may be prepared according to general methods known in the art. The esters may be prepared by condensing an appropriate w-polyhaloalkylpolythio alkanol with an appropriate acid. Acidic compounds such as acids, acid anhydrides, and acid halides may be used according to procedures known in the art. When desirable, transesterification may also be used. Etherification may be achieved with sulfate esters, active halogen compounds and the alkoxide of the w-polyhaloalkylpolythio alcohol by methods known in the art. For making some of the compounds it may be preferable to prepare the oxygen derivative first and then contact the resulting mercaptan with the desired polyhaloalkylthio or thiosulfenyl halide.

The alcohol precursors of the compounds of this invention may be prepared by reacting a mercapto alcohol with a poly-haloalkylsulfenyl or -thiosulfenyl halide. Temperatures in the range of 0 to 50 C. may be used, but ambient temperatures or somewhat lower are preferred, that is, temperatures in the range of 0 to 25 C. Various solvents may be used in the reaction which are inert to the reactants and products. Preferred solvents are halogenated hydrocarbons.

4 The following examples are offered as illustrative of the methods of preparation of the novel compounds of this invention:

EXAMPLE I A solution of 5.6 grams of 4-chlorophenylisocyanate,

10.0 grams of Z-hydroxyethyl 1,2,2,2tetrachloroethyl disulfide, and one drop of dibutyl tin dilaurate in mls. of dry benzene were allowed to stand for one week at room temperature. The solvent Was removed by distillation, the product being heated to a maximum temperature of C. at 0.4 mm. Twelve grams of 4-chlorophenylcarbam0yloxyethyl-l,2,2,2-tetrachloroetl1yl disulfide was obtained as an oil which slowly crystallized on standing.

Analysis.Theory (percent): N, 3.3. Found (percent): N, 4.1.

EXAMPLE II Into a flask fitted with condenser, thermometer, stirrer, and dropping funnel was introduced 8.5 grams of 1,1,2,2- tetrachloroethylsulfenyl chloride in 100 ml. carbon tetrachloride. Into the mixture cooled in an ice bath was added 3.3 grams of a 61% solution of 2-methoxyethyl mercaptan diluted with carbon tetrachloride. The mercaptan was added dropwise and very slowly. After addition was completed, the reaction mixture was refluxed for about 10 minutes. The mixture was then allowed to cool to room temperature and the solvent stripped under a water vacuum. The residue was distilled yielding 4 grams of methyl- ;3-(1,1,2,Z-tetrachloroethyldithio)ethyl ether boiling in a range of -100 to 117 C. at 0.4 to 0.6 mm. mercury.

Analysis.'Il1eory (percent): CI, 48.8, S, 22.1. Found (percent): CI, 46.4, S, 23.7.

The following table, Table I, lists other compounds of this invention which Were prepared according to general procedures known in the art.

TABLE I 01 s iilitl. Structure 5 (1 i Calcd. Found Caled. Found Oalcd. Found 0 O C1;SS-CHzCHz0( iCHa 39. 4 34. 3

O 0 c1,-s-s s-0H OH OiiNHCH3 4 8 0 CHCl -CHCl-S-SOHz-CHz-O-ii-NH-C1 35. 8 36. 2 3. 5 1 3. 5

O CHCI2CHCISS-OHZCH2OI (00mm 28. 1 28. 9 17.0 19.0

O O Cla-CHC1SSCH2CH2-0- OCH2CHz-S-C1 36. 2 36. 8 19. 7 10. 9

O C Cl;CHC1-SSCHz-OHgO-ilS-CHs 38. 8 41. 0 26. t 25. 5

O G Cl OHC1-S-SCH-CH:O-iiNH-Cl 58-03 3. 4 4. l

O C Gig-CHCL-S-S-CHzCHz0iiJ-NHCH3 42. 5 40. 3 19. 3 l8. 6

C C a'CHClSSCH2CH20 21192 34. 4 35. 9 15. 5 17. 1 2 7. 5 2 5. 3

0 C O1 CH.ClS-SCHr-CHz-0-iiNLl 58fi0 35. J 35. U 16. 2 16.0

O C Cl -CHClS-SCHz-CH2O-l-CH:C1 50. 3 49. 0 18. 2 20. 2

0 CHClg-CC12SsCH2CH2-O OHa 44.6 43.3 20.1 20.5

TABLE I.Continued Negative or M'P" 01 S positive Structure C. Calcd. Found Calcd. Found Galcd. Found CHClz-CCl -SSCHQOH O O-OHZ-CHZSCl 36.2 35.0 19.7 20.0

I CIIClg-CClg--SSCH2-CH2O S-Cl 39.6 34.9 21.5 23.3

CHC]gCClg-SSCH2-CH2O SC2]I5 38.8 43.2 22.4 26.4

CHCl2CC12SSCH2CII:OCNH Cl 41.3 39.2 14.9 15.6 3.3 3.1

CIlCl- CCl -S--SC1I2CII2OC-NH 41.3 39.1 14.9 15.1

01 i CHC1 C Gig-s-s-CH2C1I2-0C-NHOTI 42.5 40.1 19.3 10.9

i [CHClg-CClg-SSCHzCH20]2% 40.2 50.0 26.1 25.0

circa-CC12s-sCHz CHzO]2S O 47.5 45.3 26.8 20.7

g 011cnoC12s-SCH2CH:-OP(0 01H. 7.5 5.7

if CHC1 CClgS-S-CH:'CH2 2115 36.8 40.7 25.0 25.4

CHClg-CClr-S-SCH2CH2 H3 1 Negative. 2 Positive. The novel compounds of this invention were tested for can be determined. The results are tabulated in columns fungicidal activity against Pythium ultimum and Rhizoc- 40 I and II of Table II. tonia solani by means of the mycelial drop test. This test The novel compounds of this invention were also comis designed to measure the fungitoxic activity of fungicidal pared for fungicidal activity by means of The Standard chemicals in terms of their degree of inhibition upon Spore Slide-Germination Method for Determining Fungimycelial growth. cidal Activity. The results obtained are expressed in Each fungitoxic compound to be tested was dissolved in 5 terms of Percent lhhlhltloh of germlnatloll of fungus acetone in dilutions as indicated in the following. table. p Paper discs previously inoculated by impregnation with Each compound to be tested was dissolved in acetone in equal amounts of a particular fungus mycelium and dilutions to the desired concentration. These solutions placed on potato dextrose agar medium were treated by Were then plpetted into the wells of depression slides and applying a precise and equal volume of each of these fun- 50 allowed to dry. The Wells were filled with a spore suspengicidal solutions to their center. Following treatment with lOn Of the test organism, Monilin ia fructicola, and incuthe fungitoxic chemical, the discs were incubated along bated in a moist chamber overnight. A group of onewith inoculated but untreated control discs at ambient f Spores was exalhlned and the number of Spores temperatures until such time as these untreated control germlnated f g d WaS C unted and recorded discs were filled with mycelial growth. Activity of the fun- 55 t0 9 t h l g actlvlty in terms of the pe c gitoxic chemical tested was determined by comparative gefmlnatlon t o ent of dii of li l o th away f th The results of these tests for various chemicals of this edge of the disc in treated and untreated samples. From IHVeHtlOIl 0n the Partlculaf fungus mycelium and p re this comparison a percentage inhibition of growth area are indicated as shown in column III of Table II.

TABLE II I II III Pythium Rhizoctonia Monilinia Structure P.p.m. Percent P.p.m. Percent P.p.m. Percent l 500 100 500 100 10 100 1'ICCSSCH CII O-C-OIT 250 100 250 100 3 100 A l 125 100 150 72 1 100 C1 C1 0 I I C 500 100 500 10 100 H(J-(ll--SSCIIzCII OC-OCH2CHzS- -Cl 3 62 l |l 1,000 20 1,000 9 rroissornomoos -C1 TABLE II-Cntinued I II III Pythium Rhizoetonia Monilinia Structure P.p.m. Percent P.p.m. Percent P.p.m. Percent 1 000 100 1 000 100 H-( :oss-cmomo-c-s-om-ona E00 100 '500 38 1g 50 100 25 c1 c1 0 40 r E 1.

500 100 500 100 Hc 1- 1-s-s-omomo-o-Nn-or 250 100 250 33 a 125 11 c1 c1 1 4s 01 n 01 c 1IC|)-+SSCH2GIIzO-JJNH {3:3:::::::::::::::::::::::::::::::::::: 3 32 500 100 500 100 0 H-CS-S-CIIzCII-&NHCII3 250 100 250 100 3 l l 125 100 125 86 l 100 00 100 500 94 10 1 (H-(ECSSCHzCHzO)z-S 250 100 250 38 3 188 H 125 100 125 22 l l O 10 00 (H-CA1S-SCH2CHzO)2-S 1,000 100 1,000 97 3 67 1 500 100 500 80 1O 10 HCI-S-SCHzGH2O-I 250 79 250 3 10?) Cl C1 002KB 01 or 0 l (E l H- S-SCH CH O OCz]1 1,000 100 1,000 100 10 100 1, 000 100 1, 000 1, 000 1 1 n-o c-s-s-crncmo-om 50 100 500 78 C1 1 250 15 Aside from the specific formulation and application of the class of compounds of the invention as represented by the foregoing test, these compounds may be dispersed in or upon other inert liquid and solid carriers such as inert clay, xylenes, etc. The solid carriers may be in the form of a dust, or used in conjunction with a suitable wetting agent to form a wettable powder. The fungitoxic compounds of this invention may also be formulated with other solvents, dispersing agents, or emulsifying agents. Further, these compounds may not only be applied alone or in mixes with other compounds of the disclosed class, but may also be used in combination with other active toxicants in the formulation of fungicidal compositions.

The compounds may be applied to any environmental area which is a host to fungus or susceptible to fungus attack. For example, the fungicidal compositions may be sprayed or otherwise applied directly to a plant or other host, may be applied to the plant seed, sprayed upon the soil or other plant environment, or used in similar ways so as to effect the control of fungus and fungus caused diseases.

Obviously, many modifications and variations of the invention, as hereinabove set forth, may be made without departing from the spirit and scope thereof, and, therefore, only such limitations should be imposed as are indicated in the appended claims.

As will be evident to those skilled in the art, various modifications on this invention can be made or followed, in the light of the foregoing disclosure and discussion, without departing from the spirit or scope of the disclosure or from the scope of the following claims.

I claim:

1. Compounds having the formula ROXS R' where R represents a polyhaloalkyl group having 1 to 2 carbon atoms and 3 to 5 halogen atoms of atomic number 17 to 35, at least one of said halogens being bonded to the alpha carbon atom, X is alkylene of 1 to 4 carbon atoms, m is an integer varying from 2 to 3.

2. The compounds of claim 1 where m is 2.

3. The compounds of claim 1 where R is 1,l,2,2-tetrachloroethyl.

4. The compounds of claim 1 wherein R is trichloromethyl.

References Cited UNITED STATES PATENTS 3,203,996 7/1965 Moore 260-608 CHARLES B. PARKER, Primary Examiner D. R. PHILLIPS, Assistant Examiner 

